Dispersible, metal oxide-coated, barium titanate materials

ABSTRACT

Barium titanate-based particles having a coating comprising an oxide, hydrous oxide, hydroxide or organic acid salt of a metal other than barium or titanium, wherein at least 90 percent of said particles have a particle size less than 0.9 micrometer when said particles are dispersed by high shear mixing, useful in the fabrication of thin, fine-grained dielectric layers for multilayer ceramic capacitors with high breakdown voltage.

BACKGROUND OF THE INVENTION

[0001] The high dielectric constant of barium titanate-based materialsmake them suitable materials for multilayer ceramic capacitors, commonlyreferred to as “MLC's”. MLC's comprise alternating layers of dielectricand electrical conductor materials. Examples of MLC's are disclosed inU.S. Pat. Nos. 3,612,963 and 4,435,738. Palladium, silver,palladium-silver alloys and nickel are common electrical conductormaterials used in MLC's. The dielectric layers of an MLC are usuallyprepared from a high solids dispersion, known in the art as a “slip”.Such slips typically comprise powdered barium titanate-based materialand a polymeric binder in an aqueous or non-aqueous solvent. Films ofbinder-stabilized powder made by casting or coating with a slip aredried to provide a “green” layer of ceramic dielectric. Green layers arecoated with conductor materials in a pattern and are then stacked toprovide a laminate of alternating layers of green ceramic dielectric andconductor. The stacks are diced into MLC-sized cubes which are heated toburn off organic materials such as binder and dispersant and then firedto sinter the particles of barium titanate-based material to form acapacitor structure with laminated, dense ceramic dielectric andconductor layers. Sintering temperatures are typically in the range of1000 to 1500° C. During sintering increased ceramic dielectric densityis achieved as a result of the fusion and consolidation of the particlesto form grains. Even with the use of grain growth inhibitors, ceramicgrain size in an MLC dielectric layer is typically larger, e.g. by afactor of 3 to 5, than the size of the original primary particles.Moreover, not all porosity is removed during the sintering process.Typically, 2 to 10% porosity remains in MLC dielectric layers. Thesepores, or hole defects, in the dielectric layer, tend to be larger inlarger grain size ceramics. Certain critical capacitor properties suchas break down voltage and DC leakage are influenced by dielectricthickness, grain size and pore defects. For instance, it is believedthat effective dielectric layers need to be several, e.g. at least 3 to5, grains thick. Because a defect in any one of the layers of an MLC canbe fatal to its performance, MLC's are manufactured with a sufficientthickness of dielectric layer to effectively reduce the impact ofceramic defects which can be caused by random large grains or pores,adversely affect the properties of the MLC.

[0002] With the market demand for miniaturization in the design ofelectronic devices there is a need in the MLC industry for ceramicmaterials that will allow thinner dielectric layers without incurringthe catastrophic effects of large grain and pore size relative todielectric thickness.

[0003] Barium titanate powders produced by prior art processes, e.g.calcination or hydrothermal processes, have large particles and/orstrongly-agglomerated fine particles of a size substantially larger than1 μm and that such particles and agglomerates are not readily amenableto the production of MLC's with fine grained, ultrathin dielectriclayers, e.g. less than 4-5 μm. Thus, it would represent an advance inthe art to provide a barium titanate-based material that would besuitable for making MLC's with thinner dielectric ceramic layers, e.g.less than 4 μm, with acceptable or exceptional electrical propertiesincluding DC leakage and breakdown voltage without the need for extendedmilling.

SUMMARY OF THE INVENTION

[0004] This invention provides barium titanate-based particles having acoating comprising a metal oxide, metal hydrous oxide, metal hydroxideor organic acid salt of a metal other than barium or titanium, whereinat least 90 percent of said particles have a particle size less than 0.9micrometer when the coated particles are dispersed by high shear mixing.As used herein the term “barium titanate-based” refers to bariumtitanate, barium titanate having another metal oxide coating and otheroxides based on barium and titanate having the general structure ABO₃,where A represents one or more divalent metals such as barium, calcium,lead, strontium, magnesium and zinc and B represents one or moretetravalent metals such as titanium, tin, zirconium and hafnium. Thisinvention also provides compositions comprising such bariumtitanate-based particles of this invention, e.g. in a variety of formssuch as slurry, wet cake, powder, dispersion and slip.

[0005] Such particles are easily dispersible without the need formilling into submicron dispersions which are advantageous in themanufacture of MLC's with thin dielectric layers having submicron grainsize and high breakdown voltage. High shear mixing is effective inreducing the size of agglomerates of particles of this invention andinvolves de-agglomeration or separation of agglomerates into smallercoated particles without milling, e.g. impacting the particles withhard, milling media such as rods, balls or zirconia particles, etc.Since milling can split particles into smaller than the primary particlesize resulting in non-equiaxed particles with exposed, i.e. uncoated,surface, in a preferred embodiment the particles of this invention areunmilled, e.g. characterized by particles having a major portion of thesurface covered by the coating. In another aspect of the inventionunmilled particles are characterized as equiaxed or spherical.

[0006] Another aspect of this invention provides a method for makingsubmicron, barium titanate-based particles with a metal oxide coatingcomprising:

[0007] (a) providing submicron, barium titanate-based particles in aliquid medium,

[0008] (b) adding to the liquid medium one or more soluble metal saltsto provide submicron, particles with a coating comprising an oxide,hydrous oxide, hydroxide or organic acid salt of said metal.

[0009] Still another aspect of this invention provides a method ofmaking a dispersion of submicron, barium titanate-based particles in aliquid medium, said method comprising de-agglomerating a dispersion ofbarium titanate-based particles in the liquid medium until the particlesize distribution is less than 0.9 micrometer. Such de-agglomerating ispreferably effected by high shear mixing.

BRIEF DESCRIPTION OF THE DRAWINGS

[0010]FIGS. 1A and 1B are photomicrographs illustrating an embodiment ofbarium titanate-based particles of this invention; the illustratedparticles have a metal oxide coating and primary particle size in therange of 0.1 to 0.2 μm.

[0011]FIG. 2 is an illustration of a titration curve showing the effectof dispersing agent on the viscosity of an embodiment of a dispersion inaccordance with this invention.

[0012]FIGS. 3A and 3B are histograms showing particle size distributionof an embodiment of barium titanate particles according to thisinvention, where 3A is the particles size distribution of a dispersionas made from wet cake and 3B is the particle size distribution of thesame dispersion after high shear mixing.

[0013]FIG. 4 is a histogram showing the particle size distribution ofbarium titanate particles according to the prior art comprising stronglyagglomerated particles.

[0014]FIGS. 5A and 5B are histograms showing particle size distributionof an embodiment of barium titanate particles according to thisinvention, where 5A is the particles size distribution of a dispersionas made from wet cake and 5B is the particle size distribution of thesame dispersion after high shear mixing.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

[0015] This invention provides barium titanate-based particles having acoating comprising a metal oxide, metal hydrous oxide or metal hydroxideor mixtures thereof wherein said coated particles have a particle sizeless than 0.9 micrometer.

[0016] Such particles are easily dispersible without the need formilling into submicron dispersions which are advantageous in themanufacture of MLC's with thin dielectric layers having submicron grainsize and high breakdown voltage. High shear mixing is effective inreducing the size of agglomerates of particles of this invention andinvolves de-agglomeration or separation of agglomerates into smallercoated particles without milling, e.g. impacting the particles withhard, milling media such as rods, balls or zirconia particles, etc.Since milling can split particles into smaller than the primary particlesize resulting in non-equiaxed particles with exposed, i.e. uncoated,surface, in a preferred embodiment the particles of this invention areunmilled, e.g. characterized by particles having a major portion of thesurface covered by the coating. In another aspect of the inventionunmilled particles are characterized as equiaxed or spherical.

[0017] Such particles are useful in providing monolithic capacitorscomprising a ceramic body having a grain size of less than 0.3micrometers. Preferred MLC's exhibit an X7R temperature coefficient ofcapacitance and have a dielectric thickness of less than 4 μm and adielectric strength of at least 100 volts per μm.

[0018] Primary particle size of particles according to this invention isconveniently determined by reference to scanning electron micrographs(SEM), e.g. as illustrated by reference to FIG. 1. While it isunderstood that particles of this invention may comprise primaryparticles of varying sizes, in preferred aspects of the invention themetal oxide-coated, barium titanate-based particles have a primaryparticle size, e.g. an average primary particle size, less than 0.6 μm.In other preferred aspects of the invention the particles have a primaryparticle size of less than 0.5 micrometer, or lower, and preferably lessthan 0.4 micrometer. In even more preferred aspects of this inventionthe particles have a primary particle size of less than 0.3 micrometeror lower, and in some cases even more preferably less than 0.2micrometer.

[0019] The particles of this invention can exist as other than primaryparticles, e.g. as aggregates of primary particles and/or agglomeratesof aggregates of primary particles. SEM is not effective indistinguishing the size distribution among primary particles, aggregatesof primary particles and agglomerates of aggregates of primaryparticles. Thus, particle size distribution analysis, e.g. by lightscattering techniques, is a preferred method for characterizing theparticle size of the barium titanate-based particles of this inventionprovided that the preparation for analysis does not include treatmentthat would change the distribution of aggregated or agglomeratedparticles, e.g. de-agglomeration due to ultrasonic treatment, high shearmixing or milling. Thus, as used herein the term “particle size” is usedto refer to the size of primary particles, aggregates of primaryparticles and agglomerates of aggregates. A convenient automated lightscattering technique employs a Horiba LA-900 laser light scatteringparticle size analyzer or similar device. Such analysis typicallypresents the volume fraction, normalized for frequency, of discretesizes of particles including primary particles, aggregates andagglomerates in ten groupings, i.e. deciles, as illustrated in thehistograms of FIGS. 3-5. In more preferred aspects of this invention atleast 90 percent of the metal oxide-coated, barium titanate-basedparticles have a particle size less than 0.8 micrometer or lower, andpreferably less than 0.7 micrometer, even more preferably less than 0.6micrometer. In even more preferred aspects of this invention at least 90percent of the particles have a particle size less than 0.5 micrometeror lower, and preferably less than 0.4 micrometer, and in some caseseven more preferably less than 0.3 micrometer.

[0020] Characteristics of particle size distribution include D₉₀ whichis the smallest particle size in the decile of largest particles, D₅₀which represents the median diameter and D₁₀ which is the largestparticle size in the decile of smallest particles. The ratio of D₉₀/D₁₀is a convenient characteristic for identifying the width of the particlesize distribution curve. In various aspects of this invention theparticle size distribution is narrow, preferably having a ratio of D₉₀/D₁₀ of less than 4, more preferably less than 3 and in some cases evenmore preferably less than 2.5.

[0021] As used herein the term “dispersion” refers to two phase systemsof solid particles suspended in an liquid medium. In a preferredembodiment the stability of the dispersion, i.e. its resistance tosettling, can be enhanced by the use of a dispersing agent. A usefuldispersing agent for aqueous systems is a charged, water soluble polymersuch as a polyacrylic acid.

[0022] Except where the context is clear that a metal oxide only ismeant, as used herein the term “metal oxide” is used to describecoatings of metal oxides, metal hydroxides, hydrous metal oxides andorganic acid salts of a metal. Such organic acid salt can be convertedto an oxide or hydroxide, e.g. by thermal decomposition as occurs duringheating for ceramic binder burnout and/or ceramic sintering.

[0023] As used herein the term “high shear mixing” means mixing in aliquid medium that imparts sufficient energy to separate agglomerates ofthe coated particles of this invention into smaller particles withoutthe impact of a solid agent such as rods, cylinders or hard sphericalmedia such as zirconia spheres. Hard media is used in certain high shearmixing equipment where small sized media is used to create shear withoutimpacting. Although high shear mixing can be effected by variousequipment as described below, it is difficult to precisely define theforce applied to separate agglomerates in high shear mixing.

[0024] As used herein the term “barium titanate-based” refers to bariumtitanate, barium titanate having another metal oxide coating and otheroxides based on barium and titanate having the general structure ABO₃,where A represents one or more divalent metals such as barium, calcium,lead, strontium, magnesium and zinc and B represents one or moretetravalent metals such as titanium, tin, zirconium and hafnium. Apreferred barium titanate-based material has the structureBa_((1−x))A_(x)O.Ti_((1−y))B_(y)O₂, where x and y can be in the range of0 to 1, where A represents one or more divalent metals other than bariumsuch as lead, calcium or strontium and B represents one or moretetravalent metals other than titanium such as tin, zirconium andhafnium. Where the other metals are present as impurities, the value ofx and y will be small, e.g. less than 0.1. In other cases, other metalor metals can be introduced to provide a significantly identifiablecompound such as barium-calcium titanate, barium-strontium titanate,barium titanate-zirconate and the like. In still other cases where x ory is 1, barium or titanium can be replaced by the other metal ofappropriate valence to provide a compound such as lead titanate orbarium zirconate. In still other cases the compound can have multiplepartial substitutions of barium or titanium. An example of such multiplypartial substituted composition is represented by the structural formula

Ba_((1−x−x′−x″))Pb_(x)Ca_(x′)Sr_(x″)O.Ti_((1−y−y′−y″))Sn_(y)Zr_(y′)Hf_(y″)O₂

[0025] where x, x′, x″, y, y′ and y″ are each ≧0 and (x+x′+x″) is <1 and(y+y′+y″) is <1. In many cases the barium titanate-based material willbe disposed with a perovskite crystal structure. In many cases it ispreferred that the barium titanate material have a perovskite structure.

[0026] It has been discovered that when hydrothermally-produced, bariumtitanate particles are conventionally dried into powders, the particlesform into relatively strongly-agglomerated particles that are noteffectively de-agglomerated by simple high shear milling. Thus,dispersions made from such dry, agglomerated, barium titanate-basedpowders which have a submicron primary particle size require asubstantially long duration of impact milling to provide particles inthe micron range and longer more intense milling for submicronparticles. In contrast, agglomerated metal oxide-coated, bariumtitanate-based particles in compositions of this invention having asubmicron primary particle size, whether in a wet form such as in aslurry, wet cake, dispersion or slip or, even more surprisingly, in adry powder form, can be de-agglomerated to the submicron size range ofthe coated particles by the moderate action of high shear mixing ofdispersions comprising such particles.

[0027] The barium titanate-based particles embodied in the variousaspects of this invention can be prepared from hydrothermally-produced,barium titanate-based particles that are not dried but are maintained ina wet environment at least until the particles are provided with a metaloxide coating. Preferably, the hydrothermally-produced bariumtitanate-based particles are maintained in an aqueous slurry untilprovided with a metal oxide coating. A slurry of submicron, bariumtitanate-based particles can be prepared by a hydrothermal process, e.g.as disclosed in U.S. Pat. Nos. 4,832,939; 4,829,033; and 4,863,833. Insuch hydrothermal processes an excess amount, e.g. up to about 20 molepercent excess, of barium hydroxide solution is typically added to ahydrous titanium oxide slurry and heated, typically to a temperature inthe range of 100 to 200° C., to create submicron particles withperovskite crystalline structure. The particle size and particle sizedistribution can be manipulated by controlling process variables such astemperatures of slurry and solutions, addition rate and speed of heatingto and cooling from the perovskite forming temperature. The selection ofprocess variables for a desired particle product can be readilydetermined by those skilled in the art following general principles ofcrystallization. For instance, larger particles can be prepared byadding barium hydroxide relatively slowly to a slurry maintained at arelatively low temperature, e.g. about 35° C.; while smaller particlescan be prepared by adding barium hydroxide relatively quickly to aslurry maintained at a relatively high temperature, e.g. about 95° C.Good agitation is important for preparing uniform particles.

[0028] After the perovskite structure is imparted to barium titanateparticles by thermal treatment of a slurry, the particles are preferablywashed to remove unreacted metal species, e.g. barium ions. Washing canbe effected with ammoniated de-ionized water at pH 10 to prevent bariumfrom dissolving from the particles. The wash water can be removed byfiltration or decanting from settled particles. The number of washcycles will be determined by the purity desired in the aqueous phase,e.g. to provide a slurry in a low ion solution having a conductivityless than 5 milliSiemens, preferably less than 1 milliSiemens. Four tofive washing cycles has been found to be adequate to reduce the ioncontent of the water phase to a low level characterized by aconductivity of not more than about 100 microSiemens.

[0029] The barium titanate-based particles of this invention have acoating comprising an oxide, hydrous oxide, hydroxide or organic acidsalt of at least one metal other than barium and titanium. Usefulorganic acids, due to the low solubility of many of their metal salts,include oxalic acid, citric acid, tartaric acid and palmitic acid. It isbelieved that the organic acid salt will be converted to a metal oxideduring binder burnout. The selection of metal is preferably on the basisof enhancement imparted to the processing or properties of MLC's. Themetal in coatings is typically selected from among bismuth, lithium,magnesium, calcium, strontium, scandium, zirconium, hafnium, vanadium,niobium, tantalum, manganese, cobalt, nickel, zinc, boron, silicon,antimony, tin, yttrium, lanthanum, lead and the Lanthanide elements. Inpreferred aspects of this invention the barium titanate particles have abarium and titanium-free metal oxide coating. When ceramic capacitorswith X7R dielectric properties are desired, it is useful to provide thebarium titanate particles with dopants such as niobium oxide, tantalumoxide or neodymium oxide in combination with nickel oxide or cobaltoxide. When it is desired to provide ceramic capacitors that aresintered at relatively low temperatures, e.g. in the range of 1000 to1200° C. as compared to 1300 to 1600° C., it is useful to provide thebarium titanate particles with a dopant that promotes low temperaturesintering. Such low temperature sintering aids include bismuth oxide,zinc oxide, zinc borate, zinc vanadate, lithium borate and combinationsthereof. Dielectric-modifying and sintering temperature-lowering metaloxides can be effectively added to the barium titanate-based particlesafter the particles have been washed and prior to formation ofdispersible wet cake. Metal oxide coatings can be provided by adding toan agitated slurry of barium titanate-based particles an aqueoussolution(s) of salts, e.g. nitrates, borates, oxalates, and the like, ofmetals corresponding to the desired coating. Metal oxide precipitationto the coating is promoted by an appropriate pH, e.g. using ammoniumhydroxide. Salt solutions can be added either as one mixture of salt toform a single layer homogenous coating or separately and sequentially toform layers of individual metal oxides. In the case of metals ofrelatively higher solubility, e.g. cobalt and nickel, oxide coatingstend to be more difficult to apply and maintain withoutresolubilization; thus, it is often preferred to apply oxide coatings ofthese more soluble metals as a top coating over more readily depositedmetal oxide layers. An alkaline environment also minimizessolubilization of barium and readily provides particles with a bariumand titanium-free metal oxide coating. Metal oxide coatings of particlesintended for ceramic capacitor application typically have a thicknessless than 10 percent of the diameter of the particle, often less than 20nanometers thick, and preferably not more than 5 to 10 nanometers thick.

[0030] Slurries of metal oxide-coated, barium titanate-based particlesare conveniently produced at a relatively low level of solids, e.g. lessthan 30 wt % barium titanate-based particles. A higher levels of solids,e.g. greater than 30 wt %, is usually preferred for the production ofMLC's. Thus, in the case where a slurry of this invention is to be useddirectly in the manufacture of MLC'S, it is useful to concentrate theslurry, e.g. remove water such as by filtration, to at least 40 wt %solids or at least 50 wt %, more preferably at least 55 wt %, and insome cases, even more preferably in the range of at least about 60 or 75wt % of the particles of this invention. In some cases it may bedesirable to replace the aqueous phase with an organic liquid phase,e.g. an alcohol, by solvent exchange. Dispersing agent and binder can beadded to concentrated slurry to provide a slip or a stable dispersion ofthe barium titanate-based particles.

[0031] After a metal oxide coating is applied tohydrothermally-produced, barium titanate-based particles, the slurry canbe washed and water content of the slurry can be reduced to provide aconcentrated slurry, wet cake or powder, e.g. a moist or dry powder.Moreover, slurry, wet cake or powder can be treated with dispersingagent to provide a dispersion or also with binder and other additives toprovide a slip. Water is preferably removed by means that avoids or atleast minimizes formation of strongly-agglomerated particles, e.g.calcination. Because they are not calcined or dried, certain metaloxides may tend to remain in the form of a hydrated metal oxide whichcan be soluble if not maintained at a pH near that for minimumsolubility point for that metal oxide. For instance, nickel oxide orcobalt oxides tend to be somewhat soluble if not maintained at a pH near10. Thus, to maintain a properly coated particle, the pH of an aqueouscomponent of the compositions of this invention are preferablymaintained in the range of 9 to 11.

[0032] Slurry can also be concentrated, e.g. by filtration, to provide asolid wet cake, i.e. a non-flowing solid comprising metal oxide-coated,barium titanate-based particles and liquid. Aqueous wet cake can be in asolid state with as little as about 60 wt % solids mixed with an aqueoussolution, e.g. a solid mass of particles in a continuous liquid phase.More preferably, wet cake will comprise at least 65 wt % particles, morepreferably at least 70 wt %. Wet cake can comprise up to about 85 wt %particles, more preferably up to about 80 wt % solids, or in some casesas low as 75 wt % particles. In aqueous wet cake the aqueous solutionshould have a pH greater than 8 to inhibit metal dissolution. Apreferred pH range is 8 to 12, more preferably 9 to 11. Such wet cakemade from barium titanate-based particles is a colloidal dispersionprecursor. That is, the wet cake can be dispersed, e.g. by admixturewith a dispersing agent. Little, if any, additional liquid medium isrequired to transform a wet cake from a solid state into a fluiddispersion.

[0033] At least in the case of aqueous wet cake the particles in thecake will remain weakly-agglomerated for a relatively long time as longas the cake is maintained with a water content of at least 15 wt %, morepreferably at least 20 wt % or higher, even more preferably at least 25wt %.

[0034] A preferred embodiment of this invention provides wet cake thatis storable and transportable. Such wet cake with an extended shelf lifeis encapsulated in a moisture barrier to inhibit loss of water contentthat could promote formation of strongly agglomerated particles whichare not readily de-agglomerated. Such moisture barrier, e.g.polyethylene bags or polyethylene-coated fiber drums, can provideextended shelf life, e.g. of at least one day or more, e.g. at least 3days, more preferably longer, e.g. at least 30 days or even morepreferably at least 90 days.

[0035] Solid wet cake of this invention is readily transformed into afluid dispersion by incorporating into the cake a dispersing agentwithout a significant addition of aqueous fluid. Although fluid can beadded to the cake, the amount of dispersing agent required to transforma solid cake into a fluid dispersion is remarkably small, e.g. typicallyless than 2 wt %, based on weight of the barium titanate-based material.In some cases no additional fluid other than the fluid volume of thedispersing agent is required to transform a wet cake into a fluiddispersion. Contemplated dispersing agents are polyelectrolytes whichinclude organic polymers with anionic or cationic functional groups.Anionically functionalized polymers include carboxylic acid polymerssuch as polystyrene sulfonic acid and polyacrylic acid; cationicallyfunctionalized polymers include polyimides such as polyetherimide andpolyethyleneimine. Polyacrylic acids are preferred for manyapplications. While polymeric acid groups can be protonated, it ispreferable that such acid groups have a counter cation that will avoidreduction of dispersion pH to a level that will promote dissolution ofbarium or other metal species, e.g. as might be present in dopantcoatings. For capacitor applications a preferred cation is the ammoniumion. In some cases, it may be feasible to employ dopant metals as thecounter cation for the polymeric acid dispersant. Regardless of thedispersing agent selected the appropriate amount of dispersing agent canbe readily determined by those skilled in the art through a process oftitration to generate a curve as illustrated in FIG. 2 which shows theeffect on dispersion viscosity as a function of the amount of dispersingagent used. When the amount of dispersing agent selected is that amountwhich provides the lowest viscosity for the dispersion, theconcentration of dispersing agent can be reduced on use of thedispersion, e.g. by dilution or interaction with additives, to cause theviscosity to rise to an undesirably high level. Thus, for manyapplications it is desirable to employ a “viscosity minimizing amount”of dispersing agent which means an amount of dispersing agent thatprovides a viscosity of the ultimate dispersion in the range of theminimum viscosity and the viscosity at about the shoulder A of thetitration curve, as illustrated in FIG. 2.

[0036] A preferred dispersing agent for use in colloidal dispersionsintended for capacitor applications and for such testing has been foundto be an ammoniated polyacrylic acid having a number average molecularweight of about 8000. For instance, 0.75 wt % of such ammoniatedpolyacrylic acid (as a 40 wt % aqueous solution) has been found to beuseful for transforming wet cake into a liquid dispersion. Theincorporation of dispersing agent can be done by convenient means suchas mechanically blending dispersant into the wet cake. When high shearmixing is employed, excess dispersing agent is consumed by new particlesurface area exposed by de-agglomeration. Thus, it may be convenient toadd dispersing agent incrementally in the course of high shear mixing.

[0037] Wet cake is distinguished from slurries, dispersions, slips anddry powders in that wet cake is a non-flowing solid while slurries,dispersions and slips are fluid liquids and dry powders are flowingsolids. Moist powders may or may not flow depending on the amount ofliquid present. As more water is removed moist powder becomesprogressively drier. It is understood, however, that dry powder is notnecessarily totally dehydrated. Spray drying, freeze drying and lowtemperature vacuum-assisted drying are preferred methods for providingdry powders of metal oxide-coated, barium titanate-based particles whichremain dispersible merely by mixing into dispersing agent-containing,aqueous solution, e.g. with high shear mixing. Thus, dry powders ofmetal oxide-coated, barium titanate-based particles of this inventionare surprisingly dispersible into dispersions of submicron particleswithout the need for long duration, impact milling, e.g. impact rodmilling or vibratory milling. Unlike prior art materials, high energymilling for several hours is not required to reduce the particle size toa point where dispersions or slips of the metal oxide-coated, bariumtitanate-based particles of this invention can be used to makecapacitors with fine grained, thin dielectric layers and high breakdownvoltage.

[0038] Another aspect of this invention provides methods of making adispersion of submicron, metal oxide-coated, barium titanate-basedparticles in an aqueous solution by de-agglomerating a dispersion oflarge (greater than 1 μm), weakly-agglomerated metal oxide-coated,barium titanate-based particles until substantially all of saidparticles less than 1 μm or smaller. In a preferred method of thisinvention high solids dispersions, e.g. comprising from about 30 to 75wt % particles, are de-agglomerated by high shear mixing with adispersing agent. The optimal time for high shear mixing is readilydetermined by routine experimentation. High shear mixing can be effectedin a centrifugal pumping de-agglomerating mill as available fromSilverson Machine Inc. of East Longmeadow, Mass. Other apparatus usefulfor providing the de-agglomerated dispersions of this invention includewhat is known as supermills, colloid mills and cavitation mills.Supermills as available from Premier Mill of Reading, Pa. have amedia-filled milling chamber with high speed, rotating discs on acentral shaft. Colloid mills as available from Premier Mill of Reading,Pa. have a grinding gap between extended surfaces of a high speed rotorand a fixed stator. In cavitation mills as available from Arde BarincoInc. of Norwood, N.J., fluid is pumped through a series of rapidlyopening and closing chambers that rapidly compress and decompress thefluid imparting a high frequency shearing effect that can de-agglomerateparticles. It is expected that concentrated slurry, dispersions, wetcake, moist powder or dry powder will perform equally well in providingslips for manufacture of high performance capacitors of this invention,with a preference for dispersions, cakes or powders depending on uniquecapacitor manufacturing facilities or methods.

[0039] A defining test for weakly-agglomerated metal oxide-coated bariumtitanate-based particles of this invention comprises using a SilversonModel L4R high shear laboratory mixer equipped with a square hole highshear screen to high shear mix a 500 g sample of a dispersion comprising70 wt % of the coated particles in an alkaline aqueous solution at atemperature in the range of 25 to 30° C. and a pH at which the coatingwill not dissolve and containing an effective amount of dispersing agentfor an effective time for de-agglomerating coated particles. Aneffective amount of dispersing agent is sufficient to maintain separatedagglomerates and aggregates in the smaller particle sizes withoutre-agglomeration. An effective amount of dispersing agent will varydepending on factors such as the size of particles, the nature of thecoating and the power of the dispersing agent. An effective amount ofdispersing agent and effective time can be readily determined with a fewroutine experiments by those skilled in the art observing the effect ofthose variables, i.e. concentration of dispersing agent and high shearmixing time, on reducing the magnitude of particle size distribution. Aneffective amount of those variables will allow a particle size analysisthat reflects the true effect of high shear mixing on de-agglomeration.For many cases it had been found that an effective amount of ammoniatedpolyacrylic acid dispersing agent (number average molecular weight ofabout 8000) is 1 wt % dispersing agent per total weight of particles anddispersing agent and an effective high shear mixing time is 1 minute.

[0040] In certain aspects of this invention metal oxide-coated, bariumtitanate-based particles prepared by hydrothermal processes are, asillustrated by reference to the photomicrograph of FIG. 1, substantiallyspherical, i.e. equiaxed in appearance as opposed to having an irregularshape and/or angular surfaces common to milled and/orcalcination-derived particles. Such particles remain substantiallyspherical even after size reduction by high shear mixing. Occasionally,substantially spherical particles may be twinned, i.e. joined particlesthat grew together. The occurrence of such twinned particles isdesirably rare. The use of spherical particles, as compared tonon-spherical milled powders, provides powders characterized withexceptionally high surface area, e.g. BET surface area of at least 4square meters per gram (m²/g), or higher e.g. at least 8 m²/g or evenhigher, about 12 m²/g.

[0041] Submicron, metal oxide-coated, barium titanate particles of thisinvention are suspendable with a wide variety of binders, dispersantsand release agents using aqueous or non-aqueous solvents to provideceramic casting slips. When used in the manufacture of ceramiccapacitors, the barium titanate-based particles of this invention areconveniently dispersed, e.g. with ammoniated polyacrylic acid dispersingagent, at 50 to 80 wt % solids, in aqueous solution with from 5 to 20 wt% of dissolved or suspended, film-forming, polymeric binder to provide aslip. The film-forming polymeric binders which are popular for use inthe ceramic arts are polyvinyl acetate, polyvinylchloride, poly(vinylacetate/vinyl chloride), polyvinyl butyral, polystyrene,polymethacrylates. In some aqueous systems it is preferred to employ anemulsion of a latex binder, e.g. poly(acrylate), polystyrene acrylate),polyacrylonitrile acrylate, polyvinylchloride, polystyrene,poly(styrenebuta-diene) and carboxylated poly(styrene butadiene), e.g.as disclosed in U.S. Pat. No. 4,968,460, incorporated herein byreference. For aqueous systems, emulsions of water-insoluble polymers orwater soluble polymers, e.g. polyvinyl alcohol, are preferred.

[0042] When non-aqueous slips are preferred, the barium titanate-basedparticles are dispersed in an organic solvent containing dissolvedpolymeric binder and, optionally, other dissolved materials such asplasticizers, release agents, dispersing agents, stripping agents,antifouling agents and wetting agents. Useful organic solvents have lowboiling points and include benzene, methyl ethyl ketone, acetone,xylene, methanol, ethanol, propanol, 1,1,1-trichloroethane,tetrachloroethylene, amyl acetate, 2,2,4-triethylpentanediol-1,3-monoisobutyrate, toluene, methylene chloride, turpentineand mixtures with water such as methanol/water mixtures. Among thepolymeric materials useful in non-aqueous slips are poly(vinyl butyral),poly(vinyl acetate), poly(vinyl alcohol), cellulosic polymers such asmethyl cellulose, ethyl cellulose, hydroxyethyl cellulose,methylhydroxyethyl cellulose, polypropylene, polyethylene, siliconpolymers such as poly(methyl siloxane) and poly(methylphenyl siloxane),polystyrene, butadiene/styrene copolymer, poly(vinyl pyrollidone),polyamides, polyethers, poly (ethylene oxide-propylene oxide),polyacrylamides, and acrylic polymers such as sodium polyacrylate,poly(methyl acrylate), poly(methyl methacrylate) and copolymers such ascopolymers of ethyl methacrylate and methyl acrylate. A preferredacrylate polymer is Acryloid B-7 available from Rohm & Haas Company.Useful dispersing agents for organic solvent suspensions and slipsinclude menhadden oil, corn oil, polyethyleneimine and ammoniatedpolyacrylic acid.

[0043] Polymeric binder is useful in the range of 5 to 20 wt %.Frequently, the organic medium will also contain a small amount of aplasticizer to lower the glass transition temperature (Tg) of the binderpolymer. The choice of plasticizers is determined primarily by thepolymer which must be modified and can include phthalate esters such asdiethyl phthalate, dibutyl phthalate, dioctyl phthalate, butyl benzylphthalate, alkyl phosphates, polyethylene glycol, glycerol,poly(ethylene oxides), hydroxyethylated alkyl phenol,dialkyldithiophosphonate and poly(isobutylene).

[0044] To prepare dispersions in organic solvent, it is preferable toremove water from an aqueous wet cake of barium titanate-basedparticles, e.g. in a vacuum oven at 200° C., followed by coarsescreening, e.g. at 100 mesh. Useful suspensions can be prepared by highshear mixing barium titanate particles in a mixture organic solvent anddispersing agent. Polymeric binder and plasticizer can be added beforeor after high shear mixing. In one embodiment an organic solvent-basedslip of the invention comprises per 100 parts by weight of bariumtitanate-based particles:

[0045] 25 to 40 parts of organic solvent,

[0046] 2 to 5 parts of dispersing agnet,

[0047] 5 to 20 parts of polymeric binder, and

[0048] 0 to 15 parts of plasticizer.

[0049] With both aqueous and organic solvent-based slips, green tapescan be formed onto carrier surfaces by methods known to the skilledartisan. See, for example, J.C. Williams at page 173-197 of CeramicFabrication Processes, Volume 9 of Treatise on Materials Science andTechnology, Academic Press (1976) and U.S. Pat. Nos. 3,717,487 and4,640,905 both of which are incorporated herein by reference.

[0050] Moreover, there exists a variety of techniques for convertingslips into thin films, green layers and fired ceramics. It is believedthat the dispersions of this invention will find application, with minormodification, e.g. selection of preferred suspension medium and binder,dilution to a desired fluid viscosity, etc., in the various ceramicprocesses for making dielectric layers for MLC's. Slips can be formedinto films by spraying, layering onto a moving sheet from a waterfall ordie (such as a doctor blade) and other methods used in the MLC industry.When sufficient water is removed from the film, a cohesive, solid“green” film is provided which can be coated in a registered pattern onone or both sides with a conductor material or conductive materialprecursor, e.g. ink containing fine particles of palladium, silver,nickel or alloys of palladium and silver. Such conductive inks cancontain fine particles of the metal and ceramic. Sheets of green filmare typically stacked, e.g. up to 250 layers or more, and diced intoMLC-sized cubes which are fired to burn out polymeric binder anddispersant and sintered to form a dense multilayer capacitor structurewith fine grain structure dielectric layers. Conductive metal applied tothe ends can connect the alternating conductive interlayers forming theMLC.

[0051] The unique particle size properties of barium titanate-basedparticles of this invention are expected to allow the production ofnovel MLC's, e.g. having ultrathin layers of dielectric ceramic havingsubmicron grains. Such dielectric materials should facilitatesignificant increases in volumetric capacitance. Moreover, it isexpected that MLC's will have unexpectedly high breakdown voltage. Theabsence of large, e.g. greater than 1 μm, particles should allow for thecommercial production at high yields, e.g. greater than 98%, of MLC'scomprising multiple, e.g. greater than 40, dielectric layers. Theparticles of this invention are expected to be preferably used toproduce MLC's having a dielectric ceramic layer with a maximum grainsize is 0.9 μm or less, e.g. 0.8 μm of even smaller, say 0.7 μm. Anotheraspect of this invention provides X7R capacitors comprising more than 20dielectric layers of barium titanate-based material sintered intoceramic structure wherein said layers are less than 5 μm thick, e.g. inthe range of 2 to 4 μm thick. A higher number of dielectric layers, e.g.250 or 500, may be preferred depending on MLC design. Thin dielectriclayers allow MLC's with an increased number of dielectric layers to beused in a standard sized MLC or MLC's with a fixed number of layers tofit in a smaller sized package. The result is that the capacitance ofstandard sized MLC package can be readily increased by a factor of 5 to10 or more.

[0052] For providing monolithic X7R MLC's the particles used to make thedielectric are preferably coated with oxides of niobium, cobalt, nickeland manganese. For low fire capability, e.g. sintering at below 1200°C., a preferred metal oxide coating can also contain bismuth oxide. Toachieve ultrathin dielectric layers with a thickness less than 4micrometers, the particles preferably have a primary particle size lessthan 0.3 micrometers, e.g. in the range of 0.1 to 0.2 micrometers. Auniform, fine grain size, e.g. less than 0.3 micrometers, in ultrathindielectric layers provides superior dielectric strength in excess of 100volts per micrometer and low dissipation factor. These propertiesprovide increased reliability for high capacitance, high voltage ceramiccapacitors. The ability to provide thin dielectric layers has allowedthe production of capacitors having 5 to 10 times the capacitance for astandard case size. Such MLC's preferably comprise a monolithic ceramicbody, e.g. of metal oxide-doped barium titanate, two groups ofinterdigitated electrodes buried in said body and extending respectivelyto opposites ends of said body, and two conductive terminationscontacting said two groups respectively at said opposite ends. MLC'swith X7R characteristics have a temperature coefficient of capacitanceover a temperature range of −55° C. to 125° C. which does not vary bymore than ±15% from the capacitance at 25° C. In a preferred aspect ofthis invention the ceramic in an X7R MLC has a grain size of less than0.3 micrometers and comprises 93 to 98 weight percent of the bariumtitanate-based ceramic and 2 to 7 weight percent of other metal oxides.

[0053] The following examples illustrate the preparation of certainembodiments of various aspects of this invention but are not intended assetting forth limitations to the scope of this invention.

EXAMPLE 1

[0054] This example illustrates one hydrothermal processing method ofpreparing a slurry of barium titanate-based particles which is usefulfor preparing the coated barium titanate-based particles of thisinvention. An aqueous solution of 37 wt % titanium oxychloride (TiOCl₂)was diluted by mixing with about 9 parts of water in a reactor; ammoniumhydroxide was titrated in to pH 4 to provide a thick white gel. Thesoluble ammonium chloride was removed by filtration, followed by washingwith hot de-ionized water and reslurrying to provide a slurry of hydroustitanium oxide at 85° C. and a concentration of about 4.2 wt % astitanium dioxide. A solution of about 25 wt % barium hydroxide wasprepared dissolving barium hydroxide octahydrate in 95° C. water. Excessbarium hydroxide solution (120 mole percent) was added to the titaniumoxide slurry over a period of about 9 minutes, followed by heating to atemperature of about 200° C. to form submicron perovskite bariumtitanate particles with a narrow size distribution and equiaxedmorphology. The slurry was cooled to below 100° C. and washed with about400 liters of ammoniated de-ionized water (pH 10). The wash water wasdecanted followed by 4 more washings until the conductivity of the washwater was below 100 microSiemens. The resulting low conductivity slurrycontained barium titanate particles principally in the form ofagglomerates of substantially spherical primary particles where thetypical agglomerate particle size as determined by SEM was in the rangeof about 10 micrometers; the primary particles size as determined by SEMwas about 0.15 micrometer. Such slurries are useful source materials forapplying metal oxide coatings to provide metal oxide-coated bariumtitanate-based particles of this invention.

EXAMPLE 2

[0055] To illustrate the effect of high shear mixing on barium titanateparticles without a metal-oxide coating, a slurry produced in the mannerof Example 1 was concentrated in a filter press at a 1000 kPa (150 psi)pressure drop to provide a wet cake containing about 72 wt % solids. Thecake was dispersed in a blender with polyacrylic acid (8000 numberaverage molecular weight) as dispersing agent in an amount to provide0.75 g of polyacrylic acid per 100 g of barium titanate. The resultingdispersion had a particles size distribution with a D₉₀ of 1.8 μm. Aftera 500 g sample of the original resulting dispersion was treated for 1minute with a Silverson Model L4R high shear laboratory mixer equippedwith a square hole high shear screen operating at about 8000 rpm, theD₉₀ value was 2.1 μm.

EXAMPLE 3

[0056] This example illustrates the preparation of one embodiment ofmetal oxide-coated, barium titanate-based particles of this invention. Aslurry was prepared essentially in the manner of Example 1, containingabout 22 kg of barium titanate particles and 200 liters of ammoniatedde-ionized water at pH 10. A 1 gram-mole/kilogram (1 molal) solution ofbismuth nitrate in 2 molal nitric acid was added to the slurry in anamount to provide 3 g bismuth per 100 g barium titanate concurrentlywith a solution of 29 wt % ammonium hydroxide in an amount to maintainthe slurry at pH 10. A bismuth oxide coating readily formed on thebarium titanate particles. After addition of the bismuth solution, asolution of niobium bioxalate (about 5 wt % as niobium with excessoxalic acid) was added to the slurry of bismuth coated particles in anamount to provide 1.5 g of niobium per 100 g of barium titanateconcurrently with a solution of 29 wt % ammonium hydroxide in an amountto maintain the slurry at pH 10. A niobium oxide coating readily formedon the particles. After addition of the niobium solution, the slurry waswashed with ammoniated water and re-slurried in 200 liters of ammoniatedwater at pH 10. A solution of 1 molal cobalt nitrate in water was addedin an amount to provide about 0.18 g of cobalt per 100 g of bariumtitanate. A coating of cobalt oxide was formed on the particles. Theslurry was washed several times with ammoniated water and filtered toprovide a wet cake containing about 72 wt % of metal oxide-coated,barium titanate-based particles in a continuous phase of aqueoussolution at pH 9-10. The wet cake was dispersed using ammoniatedpolyacrylic acid essentially in the manner of Example 2 to provide adispersion of the metal oxide-coated, barium titanate particles, morethan 95 wt % of which passed through a 10 micrometer nylon mesh screen.The particle size distribution of such particles is illustrated by thehistogram of FIG. 3A. Particle size analysis indicated the mediandiameter D₅₀ was 0.64 micrometers, D₁₀ was 0.37 micrometers and D₉₀ was1.2 micrometers. The narrow particle size distribution is indicated bythe ratio of D₉₀/D₁₀ of about 3. A sample of the dispersion was treatedby high shear mixing essentially in the manner of Example 2 to reducethe size of agglomerated particles. The particle size distribution ofthe high shear mixed dispersion is illustrated by the histogram of FIG.3B. Particle size analysis indicated the median diameter was reduced to0.28 micrometers, with D₁₀ being 0.20 micrometers and D₉₀ being 0.46micrometers. The narrow particle size distribution is indicated by theratio of D₉₀/D₁₀ of about 2. About 1.2 g of a high solids dispersion (70wt % solids) of the particles was cast into a 12.5 millimeter (mm)plastic tube placed over a porous, plaster of paris mold and allowed todry in a high humidity chamber for 24 hours. A dried disk (12.5 mm indiameter by 2 mm thick) was separated from the mold and sintered at1125° C. for 2 hours to 94% theoretical density (5.64 g/cc). Thesintered barium titanate-based ceramic disk had a dielectric constant at25° C. of 2105. X7R characteristics was indicated as the thermal changein capacitance (TCC) from −55° C. to 125° C. was within the ±15%specification; TCC was −6.28 at −55° C. and 3.45 at 125° C.

EXAMPLE 4

[0057] This example comparatively illustrates the presence of stronglyagglomerated particles in dispersions prepared from dried,hydrothermally-derived, barium titanate particles as available in theprior art. A slurry of submicron, barium titanate particles was preparedessentially in the manner of Example 1 except that the slurry wasfiltered and dried to provide a dry powder. About 22 kg of powder wasthen reslurried in 200 liters of de-ionized water, ammoniated to pH 10and then doped with a metal oxide coating according to the methoddescribed in Example 3. The slurry was pressed to form a wet cake at 72wt % solids and dried. The metal oxide-coated powder was subsequentlydispersed in an aqueous solution with polyacrylic acid dispersing agentto provide a dispersion of large (greater than 10 μm) agglomerates ofstrongly agglomerated particles. Substantially all of the bariumtitanate particles were agglomerated to a size that would be retained ona 10 micrometer nylon mesh screen. After high shear mixing substantiallyall of the barium titanate particles were retained on a 5 micrometernylon mesh screen, indicating strongly agglomerated particles, e.g. thedrying of powders promotes agglomeration of particles with a relativelyhigh interparticle bond strength which are not de-agglomerated by highshear mixing. Particle size analysis indicated a trimodal distributionwith peaks at about 0.3, 1.2 and 12 micrometers, with a D₁₀ of about 0.5micrometers, a D₅₀ of about 6.4 micrometers and a D₉₀ of about 35micrometers as illustrated by the histogram of FIG. 4. The wide particlesize distribution is further characterized by a ratio of D₁₀/D₉₀ of 70.

EXAMPLE 5

[0058] This example further illustrates the preparation of a dispersionof metal oxide-coated, barium titanate-based particles according to thisinvention. A dispersion of metal oxide-coated, barium titanate particleswas prepared from wet cake essentially in the manner of Example 3 anddetermined to have a particle size distribution as illustrated in thehistograph of FIG. 5A where D₁₀ was 0.525 micrometers, D₅₀ was 1.7micrometers and D₉₀ was 4.1 micrometers. A volume of 3.8 liters (1gallon) of the dispersion was treated by high shear mixing for 45minutes in a Premier Mill supermill model HM-1.5 with recirculation at aflow rate of 30 gallons per minute; the mill was filled withyttrium-doped zirconia milling media, 0.65 millimeters in diameter. Theparticle size of the agglomerates was reduced to a particle sizedistribution as illustrated in the histograph of FIG. 5B where D₁₀ was0.13 micrometers, D₅₀ was 0.19 micrometers and D₉₀ was 0.36 micrometers.Dielectric ceramic structure made from such dispersions had a grain sizein the range of 0.2 to 0.3 μm.

EXAMPLE 6

[0059] This example illustrates the production of another embodiment ofmetal oxide-coated, barium titanate-based particles according to thisinvention. Wet cake produced essentially in the manner of Example 3 wasdried for 24 hours in a vacuum oven at 200° C. and −100 kiloPascalvacuum to provide a dispersible powder of metal oxide-coated, bariumtitanate-based powder. The powder was dispersed by mixing into anaqueous solution comprising 72 wt % solids and 0.75 wt % ammoniatedpolyacrylic acid dispersing agent. The dispersion had a particle sizedistribution with a D₉₀ of 1.9 μm. The agglomerated particles in thedispersion were reduced in size by high shear mixing for 1 minute in aSilverson Model L4R high shear laboratory mixer to provide a colloidaldispersion with a D₉₀ of 0.6 μm.

EXAMPLE 7

[0060] This example comparatively illustrates the inability of metaloxide-coated barium titanate powder of the prior art to bede-agglomerated by high shear mixing. A metal oxide-coated, bariumtitanate available from Degussa Corporation as X7R MLC Dielectric PowderAD302L (identified as having a particle size distribution with 90% lessthan 1.2 μm) was dispersed in a dispersing agent-containing aqueoussolution essentially in the manner of Example 6. The dispersed particleshad a D₉₀ of 1.8 μm and D₅₀ of 1.1 μm. After high shear mixing in aSilverson Model L4R high shear laboratory mixer for 1 minute, D₉₀ andD₅₀ were unchanged. After high energy milling for 2 hours in a vibratorymill, D₉₀ was reduced to 1.2 μm and D₅₀ was reduced to 0.7 μm.

EXAMPLE 8

[0061] This example illustrates MLC's prepared from bariumtitanate-based particles of this invention. A dispersion of metaloxide-coated, barium titanate particles prepared essentially in themanner of Example 3 was mixed with a polymeric binder and cast into thinfilms of several different thickness which was dried into green tapes.The green tapes were coated with an electrically conductive ink in anappropriate pattern, cut into slices and stacked, diced and fired at1125° C. forming MLC's having 40 ceramic dielectric layers of about 3.5,4.2 and 7.2 μm thick. The 40 Layer MLC Properties are set forth in thefollowing table where TCC is the thermal coefficient of capacitance. 40Layer MLC Properties dielectric layer thickness 7.2 μm 4.2 μm 3.5 μmDielectric constant 2265 2410 2260 Breakdown voltage 680 v 520 v 440 vTCC @ −55° C. −2.2% −6.2% −15.% TCC @ 125° C. −7.8% −14.% −2.4%

[0062] With the foregoing examples serving to illustrate a limitednumber of embodiments the full scope and spirit of the invention is setforth in the following claims.

We claim:
 1. Barium titanate-based particles having a coating comprisinga metal oxide, metal hydrous oxide, metal hydroxide or organic acid saltof a metal other than barium or titanium, wherein at least 90 percent ofsaid coated particles have a particle size less than 0.9 micrometer. 2.The barium titanate-based particles according to claim 1 having aprimary particle size less than 0.6 micrometer.
 3. The bariumtitanate-based particles according to claim 1 having a primary particlesize less than 0.5 micrometer.
 4. The barium titanate-based particlesaccording to claim 1 having a primary particle size less than 0.4micrometer.
 5. The barium titanate-based particles according to claim 1having a primary particle size less than 0.3 micrometer.
 6. The bariumtitanate-based particles according to claim 1 having a primary particlesize less than 0.2 micrometer.
 7. The barium titanate-based particlesaccording to claim 1 wherein said coated particles have a particle sizedistribution decile ratio of D₉₀/D₁₀ less than
 4. 8. The bariumtitanate-based particles according to claim 1 wherein said coatedparticles have a particle size distribution decile ratio of D₉₀/D₁₀ lessthan
 3. 9. The barium titanate-based particles according to claim 1wherein said coated particles have a particle size distribution decileratio of D₉₀/D₁₀ less than 2.5.
 10. The barium titanate-based particlesaccording to claim 1 wherein at least 90 percent of said coatedparticles have a particle size less than 0.8 micrometer when saidparticles are dispersed by high shear mixing.
 11. The bariumtitanate-based particles according to claim 1 wherein at least 90percent of said coated particles have a particle size less than 0.7micrometer when said particles are dispersed by high shear mixing. 12.The barium titanate-based particles according to claim 1 wherein atleast 90 percent of said coated particles have a particle size less than0.6 micrometer when said particles are dispersed by high shear mixing.13. The barium titanate-based particles according to claim 1 wherein atleast 90 percent of said coated particles have a particle size less than0.5 micrometer when said particles are dispersed by high shear mixing.14. The barium titanate-based particles according to claim 1 wherein atleast 90 percent of said coated particles have a particle size less than0.4 micrometer when said particles are dispersed by high shear mixing.15. The barium titanate-based particles according to claim 1 wherein atleast 90 percent of said coated particles have a particle size less than0.3 micrometer when said particles are dispersed by high shear mixing.16. The barium titanate-based particles according to claim 1 whereinsubstantially all of said particles are equiaxed or spherical.
 17. Aslurry, dispersion or slip comprising at least 50 weight percent of saidcoated particles according to claim 1 .
 18. The slip according to claim17 further comprising between 3 and 20 weight percent of a bindercomposition comprising a dissolved or suspended, film-forming, polymer.19. A wet cake comprising coated particles according to claim 1 andbetween 15 and 35 weight percent of an aqueous liquid.
 20. The wet cakeof claim 19 further comprising a moisture barrier that provides shelflife such that after 30 days said wet cake is dispersible by theadmixture of a dispersing agent by high shear mixing into an aqueousdispersion of the coated particles, 90 percent of which have a particlesize less than 1 micrometer.
 21. Barium titanate-based particles havinga primary particle size less than 0.6 micrometer and a coatingcomprising an oxide, hydrous oxide, hydroxide of at least one metalselected from the group consisting of lithium, magnesium, calcium,strontium, scandium, zirconium, hafnium, vanadium, niobium, tantalum,manganese, cobalt, nickel, zinc, boron, silicon, antimony, tin, yttrium,lanthanum, lead, bismuth or a Lanthanide element, wherein at least 90percent of the coated particles have a particle size less than 0.9micrometer.
 22. The barium titanate-based particles according to claim21 having a primary particle size less than 0.5 micrometer.
 23. Thebarium titanate-based particles according to claim 21 having a primaryparticle size less than 0.4 micrometer.
 24. The barium titanate-basedparticles according to claim 21 having a primary particle size less than0.3 micrometer.
 25. The barium titanate-based particles according toclaim 21 having a primary particle size less than 0.2 micrometer. 26.The barium titanate-based particles according to claim 21 wherein saidcoated particles have a particle size distribution decile ratio ofD₉₀/D₁₀ less than
 4. 27. The barium titanate-based particles accordingto claim 21 wherein said coated particles have a particle sizedistribution decile ratio of D₉₀/D₁₀ less than
 3. 28. The bariumtitanate-based particles according to claim 21 wherein said coatedparticles have a particle size distribution decile ratio of D₉₀/D₁₀ lessthan 2.5.
 29. The barium titanate-based particles according to claim 21wherein at least 90 percent of said coated particles have a particlesize less than 0.8 micrometer when said particles are dispersed by highshear mixing.
 30. The barium titanate-based particles according to claim21 wherein at least 90 percent of said coated particles have a particlesize less than 0.7 micrometer when said particles are dispersed by highshear mixing.
 31. The barium titanate-based particles according to claim21 wherein at least 90 percent of said coated particles have a particlesize less than 0.6 micrometer when said particles are dispersed by highshear mixing.
 32. The barium titanate-based particles according to claim21 wherein at least 90 percent of said coated particles have a particlesize less than 0.5 micrometer when said particles are dispersed by highshear mixing.
 33. The barium titanate-based particles according to claim21 wherein at least 90 percent of said coated particles have a particlesize less than 0.4 micrometer when said particles are dispersed by highshear mixing.
 34. The barium titanate-based particles according to claim21 wherein at least 90 percent of said coated particles have a particlesize less than 0.3 micrometer when said particles are dispersed by highshear mixing.
 35. The barium titanate-based particles according to claim21 wherein substantially all of said particles are equiaxed orspherical.
 36. A slurry, dispersion or slip comprising at least 50weight percent of said coated particles according to claim 21 .
 37. Theslip according to claim 36 further comprising between 3 and 20 weightpercent of a binder composition comprising a dissolved or suspended,film-forming, polymer.
 38. A wet cake comprising coated particlesaccording to claim 21 and between 15 and 35 weight percent of an aqueousliquid.
 39. The wet cake of claim 38 further comprising a moisturebarrier that provides shelf life such that after 30 days said wet cakeis dispersible by the admixture of a dispersing agent by high shearmixing into an aqueous dispersion of the coated particles, 90 percent ofwhich have a particle size less than 1 micrometer.
 40. Non-milled bariumtitanate-based particles having a coating comprising a metal oxide,metal hydrous oxide, metal hydroxide or organic acid salt of a metalother than barium or titanium, wherein at least 90 percent of saidcoated non-milled particles have a particle size less than 0.9micrometer when said coated non-milled barium titanate-based particlesare dispersed by high shear mixing.
 41. The non-milled bariumtitanate-based particles according to claim 40 having a primary particlesize less than 0.6 micrometer.
 42. The non-milled barium titanate-basedparticles according to claim 40 having a primary particle size less than0.5 micrometer.
 43. The non-milled barium titanate-based particlesaccording to claim 40 having a primary particle size less than 0.4micrometer.
 44. The non-milled barium titanate-based particles accordingto claim 40 having a primary particle size less than 0.3 micrometer. 45.The non-milled barium titanate-based particles according to claim 40having a primary particle size less than 0.2 micrometer.
 46. Thenon-milled barium titanate-based particles according to claim 40 whereinsaid coated non-milled particles have a particle size distributiondecile ratio of D₉₀/D₁₀ less than
 4. 47. The non-milled bariumtitanate-based particles according to claim 40 wherein said coatednon-milled particles have a particle size distribution decile ratio ofD₉₀/D₁₀ less than
 3. 48. The non-milled barium titanate-based particlesaccording to claim 40 wherein said coated non-milled particles have aparticle size distribution decile ratio of D₉₀/D₁₀ less than 2.5. 49.The non-milled barium titanate-based particles according to claim 40wherein at least 90 percent of said coated non-milled particles have aparticle size less than 0.8 micrometer when said particles are dispersedby high shear mixing.
 50. The non-milled barium titanate-based particlesaccording to claim 40 wherein at least 90 percent of said coatednon-milled particles have a particle size less than 0.7 micrometer whensaid particles are dispersed by high shear mixing.
 51. The non-milledbarium titanate-based particles according to claim 40 wherein at least90 percent of said coated non-milled particles have a particle size lessthan 0.6 micrometer when said particles are dispersed by high shearmixing.
 52. The non-milled barium titanate-based particles according toclaim 40 wherein at least 90 percent of said coated non-milled particleshave a particle size less than 0.5 micrometer when said particles aredispersed by high shear mixing.
 53. The non-milled barium titanate-basedparticles according to claim 40 wherein at least 90 percent of saidcoated non-milled particles have a particle size less than 0.4micrometer when said particles are dispersed by high shear mixing. 54.The non-milled barium titanate-based particles according to claim 40wherein at least 90 percent of said coated non-milled particles have aparticle size less than 0.3 micrometer when said particles are dispersedby high shear mixing.
 55. The non-milled barium titanate-based particlesaccording to claim 40 wherein substantially all of said non-milledparticles are equiaxed or spherical.
 56. A slurry, dispersion or slipcomprising at least 50 weight percent of said coated non-milledparticles according to claim 40 .
 57. The slip according to claim 56further comprising between 3 and 20 weight percent of a bindercomposition comprising a dissolved or suspended, film-forming, polymer.58. A wet cake comprising coated non-milled barium titanate-basedparticles according to claim 40 and between 15 and 35 weight percent ofan aqueous liquid.
 59. The wet cake of claim 58 further comprising amoisture barrier that provides shelf life such that after 30 days saidwet cake is dispersible by the admixture of a dispersing agent by highshear mixing into an aqueous dispersion of the coated non-milledparticles, 90 percent of which have a particle size less than 1micrometer.
 60. Barium titanate-based particles having a coatingincluding more than one layer having a different composition, the layerscomprising a metal oxide, metal hydrous oxide, metal hydroxide ororganic acid salt of a metal.
 61. The barium titanate-based particles ofclaim 60 , wherein the layers comprise an oxide, hydrous oxide,hydroxide or organic acid salt of at least one metal selected from thegroup consisting of lithium, magnesium, calcium, strontium, scandium,zirconium, hafnium, vanadium, niobium, tantalum, manganese, cobalt,nickel, zinc, boron, silicon, antimony, tin, yttrium, lanthanum, lead,bismuth or a Lanthanide element.
 62. The barium titanate-based particlesof claim 61 , wherein the layers comprise an oxide, hydrous oxide,hydroxide or organic acid salt of at least one metal selected from thegroup consisting of magnesium or yttrium, manganese.
 63. The bariumtitanate-based particles of claim 60 , wherein at least 90 percent ofsaid coated particles have a particle size less than 0.9 micrometer. 64.The barium titanate-based particles of claim 60 , wherein the coatinghas a thickness of less than 20 nanometers.